MX2007014697A - Bacterial cellulose-containing formulations and method of producing effective bacterial cellulose-containing formulations. - Google Patents

Abstract

New formulations of bacterial cellulose and a new method to produce formulations of bacterial cellulose that exhibit improved viscosity-modifying properties particularly with low energy applied to effectuate viscosity changes therewith is provided. Such a method includes the novel co-precipitation with a water soluble co-agent that permits precipitation in the presence of excess alcohol to form an insoluble fiber that can than be utilized as a thickener or suspension aid without the need to introduce high energy mixing. Such bacterial cellulose properties have been available in the past but only through highly labor and energy intensive processes. Such an inventive method as now proposed thus provides a bacterial cellulose-containing formulation that exhibits not only properties that are as effective as those for previous bacterial celluloses, but, in some ways, improvements to such previous types. Certain end-use compositions and applications including these novel bacterial cellulose-containing formulations are also encompassed within this invention.

Description

FORMULATIONS CONTAINING BACTERIAL CELLULOSE AND PAR METHOD TO PRODUCE EFFECTIVE FORMULATIONS CONTAINING CELLULOSE BACTERIAL FIELD OF THE INVENTION (The present invention relates generally to a new method for producing cellulose formulations Bacterial I exhibited improved properties that modify the viscosity, particularly by applying low energy to effect changes in the viscosity therewith. Such a method includes the new co-precipitation with a water-soluble co-agent that allows precipitation in the presence of alcohol and d intensive energy. Such an inventive method as is now proposed thus provides a formulation containing bacterial cellulose that exhibits not only properties as effective as those of the previous bacterial celluloses, but, in some way, improves upon such previous types. Certain compositions and end-use applications including these new formulations containing bacterial cellulose are also framed within this invention.

- - ! BACKGROUND OF THE INVENTION Bacterial cellulose is a broad category of polysaccharides that exhibit highly desirable properties, even when such compounds are essentially the same chemical structure as celluloses derived from plant material. However, as the name implies, the source of these polysaccharides is bacterial in nature (usually produced by microorganisms of the genus Acetobacter) as a result of fermentation, purification,? and recovery of them. Such bacterial cellulose compounds are comprised of very fine cellulosic fibers having dimensions and ratios between unique dimensions (diameters from about 40 to 100 nm each and lengths from 0.1 to 15 microns) in the form of bundles (with a diameter of 0.1 to 0.2 microns on average). Such a structure of entangled bundles forms a lattice network structure that facilitates the increase of volume when it is in an aqueous solution thus providing excellent three-dimensional networks. The three-dimensional structures effect an appropriate and desirable viscosity modification as well as suspension capacities through the construction of a creep tension system within a target liquid as well as an excellent apparent viscosity. Such a result thus allows the highly effective suspension of materials (such as food, as a - - example) that are prone to settle over time outside the solution, particularly in aqueous solutions. Additionally, such bacterial cellulose formulations help by preventing the settling and separation of fast-prepared liquid foods (ie, soups, chocolate drinks, yogurt, juices, dairy products, cocoas, and the like) although with the need to employ amounts of relatively high energy through mixing or heating i to initially reach the desired level of suspension I for such foods. The resulting fibers (and thus the bundles) are insoluble in water and, with the capabilities described above, exhibit thickening properties of polyol and water. A particular type of bacterial cellulose, micro fibrillated cellulose, is normally provided in a neutral state and exhibits the ability to associate without any added influence. However, without any such extra additives to effect thickening or other type of viscosity modification, it has been observed that the resulting systems will exhibit by themselves high degrees of instability, particularly over periods of time associated with the typical requirements. of shelf life of food. As a result, certain co-agents, such as carboxymethyl cellulose (CMC), also known as cellulose gum, have been introduced into cellulose products - - bacterial through adsorption on its fibers, followed by spray drying (without any co-precipitation stage) in order to provide improvements in stabilization and dispersion, more likely through the presence of negative charges in the CMC transferred to the same fibers of bacterial cellulose. Therefore, such charges appear to provide rejection capabilities to prevent fiber bundles from reaming the formed network. Even with such a possibility, it is known that the selection of an appropriate CMC greatly affects the rheological properties resulting from the target bacterial cellulose due to the sensitivity of certain CMC products to salt and acid. As such, even though I know they have provided improvements in the use of bacterial cellulose with such CMC inclusions in the past, great care must be taken to ensure that the appropriate pH level and salinity conditions are adequate for the entire formulation. For this reason, they are of great interest for: the target industries, additional improvements to allow greater reliability in the use of bacterial cellulose in thousands of applications. Aditionally, although such bacterial celluloses are of great interest and importance in providing effective rheological modifications within liquid-based foods, for the reasons mentioned above, it has been found that the costs associated with the production of - - i? Such cellulosic materials are very high, particularly in terms of the necessary work and waste problems that result from them. The fermentation of such materials initially produces very low amounts. Generally, the method of producing purification and recovery of such bacterial cellulose materials causes a problematic series of steps after completing the fermentation in order to produce a wet mass with a sufficient amount of bacterial cellulose product in terms of efficiency from of the initial fermentation. In addition, spray drying can also affect the final recovery performance of bacterial cellulose during the production of powders. Such excessive stages are not only intense work and energy but also result in large quantities of wastewater and waste materials that require disposal and management. As such, the production costs of bacterial cellulose (in particular micro fibrillated cellulose) have proven to be excessively high relative to other gums, thus restricting the use of such a product within certain desirable end uses.

Currently, no effective method that has remedied these problems has been developed, let alone a method that will ultimately provide a bacterial cellulose material that exhibits certain improved properties within applications. 1 - - objective in comparison with the materials produced through the aforementioned traditional production method. ! SUMMARY OF THE INVENTION Accordingly, this invention encompasses a method for the production of a bacterial cellulose-containing formulation comprising the steps of a) providing a bacterial cellulose product through fermentation; b) optionally lysing the bacterial cells of the resulting bacterial cellulose product; c) mixing said bacterial cellulose resulting from either the product of step "a" or "b" with a polymeric thickener selected from the group consisting of at least one charged cellulose ether, at least one precipitating agent, and any combination thereof; and d) co-precipitating the mixture of step "c" with a water-miscible non-aqueous liquid (such as, as a non-limiting example, an alcohol). The possible cellulose ether I charged from step "c" is a compound used to disperse and stabilize the crosslinked network in final end-use compositions to which such a formulation containing bacterial cellulose is added. The favillite charged compounds, as alluded to above, the ability to form the necessary fiber network through the rejection of individual fibers. The possible precipitation agent of stage "c" is a compound used to preserve the functionality of bacterial cellulose fiber - - reticulated during drying and grinding. Examples of such charged cellulose ethers include such cellulose-based compounds that exhibit either a positive or negative total, and include, without limitation, any sodium carboxymethyl cellulose (CMC), cationic hydroxyethyl cellulose, and the like. The precipitation agent (drying) is selected from the group of natural and / or synthetic products including,! Without limitation, xanthan products, pectin, alginates, gelatin gum, welan gum, diutan gum, rhamsan gum, carrageenan, guar gum, agar, gum arabic, ghatti gum, karaya gum, gum tragacanth, tamarind gum, j locust bean gum and the like. Preferably, but not necessarily, for reasons associated with the ability to reactivate bacterial cellulose after spray drying and prior to incorporation into a target liquid to be rheologically modified therewith, a precipitating agent is included (drying ). Thus, a more specific method encompassed within this invention comprises the steps of a) providing a bacterial cellulose product through fermentation; b) optionally lysing the bacterial cells of the bacterial cellulose product; c) mixing said bacterial cellulose product resulting from any of the steps "a" or "b" with a biogoma (which, if incorporated as a fermentation broth will have preferably the bacterial cells Used from the same); and d) co-precipitating the mixture of step "c" with a nonaqueous liquid miscible with water. Alternatively, such a specific method may comprise the steps of a) providing a bacterial cellulose product through fermentation; b) mixing said bacterial cellulose product with a biogoma; c) co-lysing the mixture of step i "b" to remove the bacterial cells therefrom; and d) co-precipitating the mixture of step "c" with a non-aqueous liquid miscible with water. The resulting co-precipitated product will be found in the form of a pressed mass that I can then be dried and the particles obtained therefrom can then be crushed to a desired particle size. Also, for! certain applications, the particles can then be mixed with another hydrocolloid, such as carboxymethylcellulose (CMC), to provide certain properties, In addition, an inventive product of this development would be defined as a formulation containing bacterial cellulose comprising at least one material of bacterial cellulose and at least one polymeric thickener I selected from the group consisting of at least one charged cellulose ether, at least one precipitating agent selected from the group consisting of xanthan products, pectin, alginates, gelatin gum, welan gum , gum diutan, I rhamsany gum carrageenan, guar gum, agar, gum arabic, - - i ghatti gum, [karaya gum, gum tragacanth, tamarind gum, locust bean gum and the like, and any mixture thereof, wherein said formulation exhibits a viscosity capacity of at least 300 cps and a yield stress measurement of 1.0 dynes / cm2 when a quantity (of at most 0.36% by weight of a water sample of 500; ml and after application of at most 2 passes at 1500 psi in an extensional homogenizer) is introduced into I. In a potentially preferred embodiment, the bacterial and xanthan cellulose formulation produced in this way has the distinct advantage of facilitating activation without requiring any intense work or energy activation.Another distinct advantage of this total method is the ability to collect the formulation that contains bacterial cellulose resulting from precipitation with isopropyl alcohol, either with a charged cellulose ether or a precipitating agent (dried) present in the the same Therefore, since bacterial cellulose is co-precipitated in the manner described above, the polymeric thickener insoluble in alcohol (such as xanthan or sodium CMC), without attempting to be bound by any specific scientific theory, appears to provide protection. to the bacterial cellulose by providing a coating on at least a portion of! the resulting fibers formed therefrom. So, apparently the polymeric thickener actually helps I I ii associating and dewatering the cellulosic fibers to the addition of a non-aqueous liquid (such as preferably a lower alkyl alcohol), thus resulting in the collection of substantial quantities of the low yielding polysaccharide during such a co-precipitation step. Avoiding substantial quantities of water during the purification and recovery steps thus allows for the final collection of large quantities of bacterial cellulose. With this new process, the highest amount of fermented bacterial cellulose can be collected, thus providing the high efficiency in the desired production, as well as avoiding, as mentioned above, wastewater and multiple drainage and re-mixing passes typically required to obtain such a resulting product. In addition, as previously described, the presence of a drying agent, in particular, as an example, does not! limiting, a xanthan product, as a coating on at least a portion of the bacterial cellulose fiber bundles, appears to provide an improvement in the activation requirements when introduced into a target end-use composition. Surprisingly, there is a remarkable reduction in the energy required to effect the benefits in the rheological modification deduced according to the bacterial cellulose-containing formulation of this invention compared to the previously-produced products in Similary. Also, since bacterial cellulose (ie, micro fibrillated cellulose, hereinafter referred to as "MFC") provides unique functionality and rheology compared to a soluble polymeric thickener alone, the resulting product I produced through this method of invention? allows a lower cost alternative to typical processes with improvements in the reactivation requirements, resistance to viscosity changes during food processing at high temperatures, and improved suspension properties during shelf storage for long periods. DETAILED DESCRIPTION OF THE INVENTION For the purposes of this invention, the term "formulation" containing bacterial cellulose "is intended to encompass a bacterial cellulose product produced by the method of the invention and therefore includes a xanthan product which overlays at least a portion of the resultant bacterial cellulose fiber bundles. The term "formulation"; it is therefore intended to convey that the product produced therefrom is a combination of bacterial cellulose and xanthan produced in such a manner and exhibiting such resulting structure and configuration. The term "bacterial cellulose" is intended to encompass any type of cellulose produced through the fermentation of a bacterium of the Acep'obacter genus and includes materials popularly referred to as micro fibrillated cellulose, cellulose - - bacterial reticulate, and the like. As noted above, bacterial cellulose can be used as an effective rheological modifier in various compositions. Such materials, when dispersed in fluids, produce thixotropic, highly viscous mixtures possessing high yield stress. The yield stress is a measure of the force required to initiate a flow in a system; type gel. It is indicative of the suspension capacity of [a fluid, as well as indicative of the ability of the fluid to remain in situ after its application to a vertical surface. Typically, such rheological modification behavior is provided through some degree of processing of a mixture of the bacterial cellulose in a hydrophilic solvent, such as water, polyols (eg, ethylene glycol, glycerin, polyethylene glycol, etc.), or mixtures thereof. ! This process is called "activation" and generally comprises high pressure homogenization and / or high cut mixing. However, it has been found that the formulations of the invention containing bacterial cellulose are activated in low energy mixing. Activation is a process in which the three-dimensional structure of cellulose is modified in such a way that cellulose imparts functionality to the base solvent or solvent mixture in which activation occurs, or to a composition - - to which the activated cellulose is added. The functionality includes providing properties such as thickness, imparting creep tension, thermal stability, suspension properties, freeze-thaw stability,; flow control, foam stabilization, formation of: coating and film, and the like. The process ! followed during the activation process does significantly more than just disperse the cellulose in the base solvent. Such processing "unravels" the cellulose fibers to expand the cellulose fibers. The formulation containing bacterial cellulose can be used in the form of a wet mix (dispersion) or as a dried product, produced by drying the dispersion using well-known drying techniques, such as spray drying, or drying by, freezing to impart the rheological benefits desired to a target fluid composition. Activation of: bacterial cellulose (such as MFC or cross-linked bacterial cellulose) expands the cellulose portion to create a network of highly interlaced crosslinked fibers with a very high surface area. Activated crosslinked bacterial cellulose has an extremely high surface area which is believed to be at least 200 times higher than conventional micro crystalline cellulose (i.e., cellulose provided by plant sources). The bacterial cellulose used in this I j l ? it can be from; any type associated with the fermentation product of microorganisms of the genus Acetobacter, and was previously available, as an example, in CPKelco U.S. 'under the trade name CELLULON®. Such aerobic culture products are characterized by a network of interconnected, highly cross-linked, branched fibers which are insoluble in water. The preparation of such bacterial cellulose products is well known. For example, the U.S. Patent. No. 5, 079, 162; and the U.S. Patent. No. 5, 144, 021, both incorporated herein by reference, describe a method and means for: producing aerobicically cross-linked bacterial cellulose under agitated culture conditions, using a bacterial species of Acetobacter aceti var. Xylinum The use of agitated culture conditions results in the sustained production, on an average of 70 hours, of at least 0.1 g / liter per hour of the desired cellulose. The cross-linked cellulose of moist mass, containing about 80-85% water, can be produced using the methods and conditions described in the aforementioned patents, i Dry cross-linked bacterial cellulose can be produced using drying techniques, such as drying and spray, or freeze drying, which are well known. | The 'Acetobacter is characteristically a bacterium gram negative; in the form of a bar of 0.6-0.8 microns per 1.0-4 microns. It is a strictly aerobic organism; that is, his metabolism is respiratory, not fermentative. This bacterium is further distinguished by the ability to produce multiple poly-ß-1, 4-glucan chains, chemically identical to cellulose. The chains of micro cellulose, or micro fibrils of cross-linked bacterial cellulose are synthesized on the surface of the bacterium, at sites outside the cell membrane.

These microfibrils generally have cross-sectional dimensions of approximately 1.6 nm by 5.8 nm. In contrast, b, under static or stopped culture conditions, the microfibrils on the surface of the bacterium combine to form a fibril having in general cross-sectional dimensions of about 3.2 nm by 133 nm. The small cross-sectional size of these fibrils produced with Acetobacter, together with the concomitantly large surface and the inherent hydrophilicity of the cellulose, provides a cellulose product that has an unusual high capacity to absorb aqueous solutions.

Additives have frequently been used in combination with I the crosslinked bacterial cellulose to aid in the formation of stable viscous dispersions. The aforementioned problems inherent in the purification and collection of such bacterial cellulose have led to the determination that the method employed in the present provides excellent results to the desired degree. The first step in the whole process is to provide any amount of the target bacterial cellulose in fermented form.; The production method for this stage was described above. The performance of such a product has proven very difficult to generate at highly consistent levels, therefore it is imperative to achieve the retention of the target product in order to finally provide a re-packaged product at the lowest cost. The purification of such materials is well known. The lysate of the bacterial cells of the bacterial cell product is achieved through the introduction of a caustic, such as sodium hydroxide, or any I similar additive with high pH (above about 12. 5 pH,; preferably) in an amount to properly remove as many expired bacterial cells as possible from the cellulosic product. This can be followed in more than one stage if desired. Then, neutralization with an acid typically follows. Any suitable acid of pH and molarity may be used sufficiently low to combat (and thus effectively neutralize or reduce the pH level of the product as close to 7.0 as possible). Sulfuric, hydrochloric, and nitric acid are suitable examples for such a step. The one of ordinary experience in the technique will easily determine the selection appropriate and quantity of such reagent for such purpose. Alternatively, the cells can be lysed and digested by enzymatic methods (treatment with lysozyme and protease at the appropriate pH). Then, the lysed product is subjected to mixing with a polymeric thickener in order to effectively coat the fibers and target the bacterial cellulose. The polymeric thickener must be insoluble in alcohol (in particular isopropyl alcohol). Such a thickener is either an aid for the dispersion of the bacterial cellulose within the target fluid composition, or an aid in the drying of the bacterial cellulose to remove water from it more easily, as well as to potentially aid in the dispersion or suspension of the fibers within a target fluid composition. Suitable dispersing aids (agents) include, without limitation, CMC (of various types), patterned HEC, etc., essentially any compound of polymeric nature and exhibiting the dispersing capabilities necessary for bacterial cellulose fibers when introduced within the objective liquid solution. Preferably such dispersion aid is CMC, such as CEKOL® available from CP Kelco. The appropriate precipitation adjuvants (agents), as described above, include any number of biogomes, including xanthan products (such as KETROL®, KETROL T®, and the like of CP).

Kelco) gellan gum, welan gum, diutan gum, rhamsan gum, guar, locust bean gum, and the like, and other types of natural poiimeric thickeners, such as pectin, as a non-limiting example. Preferably, the polymeric thickener is < a xanthan product and it is introduced and mixed with the bacterial cellulose in broth form. Basically, the mixture of both products in the form of broth, powder or powder rehydrate, allows the desired generation of a coating | of xanthan in at least a portion of the fibers and / or bundles of bacterial cellulose. In one embodiment, the bacterial and xanthan cellulose broths are subsequently mixed until purification (lysate) of both to remove: residual bacterial cells. In another embodiment, the broths can be mixed together without being used initially, but co-lysates during mixing for such purification to occur. The quantities of each component within the method can vary considerably. For example, bacterial cellulose will typically be present in an amount of from about 0.1% to about 5% by weight of the added polymeric thickener, preferably from about 0.5% to about 3.0%, while the polymeric thickener can be present in an amount from 10 to about 900% by weight of the bacterial cellulose. , After mixing and coating the bacterial cellulose with the polymeric thickener, the resulting product is then collected by co-precipitation in a liquid; non-aqueous miscible in water. Preferably, for reasons of toxicity, availability, and cost, such a liquid is an alcohol, such as, as more preferred, isopropyl alcohol. Likewise other types of alcohols, such as ethanol, methanol, butanol, and the like can be used, not to mention! other non-aqueous liquids miscible in water, such as acetone, ethyl acetate, and any mixture thereof. Any mixture of such non-aqueous liquids can also be used, for such a co-precipitation stage. In general, the co-precipitated product is processed through a solid-liquid separation apparatus, allowing the removal of the alcohol-soluble components, and, leaving the formulation containing bacterial cellulose in it. From there, a product is collected in the form of a wet mass and then transferred to a drying apparatus and subsequently crushed for the production of appropriately sized particles. Additional co-agents may be added to the wet mass or to the dry materials in order to provide additional properties and / or benefits. Such co-agents include vegetable, algae and bacterial polysaccharides and their derivatives together with weight-bearing carbohydrates. lower molecular weight such as sucrose, glucose, maltodextrin,; and the similar. Other additives may be present within the bacterial cellulose-containing formulation including, without limitation, a hydrocolloid, polyacrylamides (and homologs), polyacrylic acids (and homologs), polyethylene glycol, poly (ethylene oxide), polynylalcohol, polyvinylpyrrolidones, starch (and similar sugar-based molecules), modified starch, gelatin of animal origin, and uncharged cellulose ethers (such as carboxymethylcellulose, hydroxyethylcellulose, and the like). The bacterial cellulose-containing formulations of this invention can then be introduced into a plethora of possible foods, including beverages, frozen products, cultured dairy products, and the like; compositions, not food, such as household cleaners, fabric softeners, hair conditioners, hair styling products, or as stabilizers or formulating agents for asphalt emulsions, pesticides, corrosion inhibitors in metal working, manufacturing latex, as well as in applications; for paper and non-textiles, biomedical applications, pharmaceutical excipients, and fluids for oil drilling, etc. The fluid compositions that I include this; formulation of the invention, prepared as described above, may include such formulations containing bacterial cellulose in an amount of from about 0.01% to about 1% by weight, and preferably from about 0.03% to about 0.5% by weight, of the total weight of the fluid composition. The formulation containing bacterial cellulose finally produced detj > and imparting a viscosity modification to the water sample of 500 ml (when added in an amount of at most 0j36% by weight thereof) of at least 300 cps as well as a measure of yield stress within the same sample test of at least 1.0 dynes / cm2. Preferred Modes of the Invention The following non-limiting examples provide teaching 1 of various methods encompassed within this invention. EXAMPLE 1 MFC was produced in a 1200 gal. Thermenator with a final yield of 1.49% weight. The broth was treated with 350 ppm hypochlorite and subsequently treated with 70 ppm lysozyme and 19.4 ppm protease. A portion of the treated MFC broth was mixed with a given amount of xanthan gum broth (MFG / XG = 2/1, dry base) and then the resulting mixture was precipitated with isopropyl alcohol (85%) to form a pressed mass. A portion of the pressed mass was dried in an oven at 70 ° C for 2 hours and crushed in - - a Brinkmann Mill to 60 mesh. The powder formulation was then introduced into a solution (500 ml) of standard water and stream (ST, 2,782 g of CaCl2.2H20 and 18,927 g of NaCl are dissolved in 5 gal of deionized water) in an amount of about 0.36. % by weight thereof, with 20% by weight of carboxymethylcellulose (CMC) added simultaneously (resulting in amounts of 0.288% MFC / Xanthan and (0.072% CMC), and the composition was then mixed with a Silverson mixer at 8000 rpm for 10 minutes The viscosity of the product (measured by means of the Brookfield viscometer, Axis 61 at 5 rpm for 1 minute) and the yield stress was 1176 cP and 4.91 dynes / cm2, respectively. 210 ml of the resulting activated MFC solution (0.36%) with 15.5 grams of sand classified (through 60 mesh but in mesh 80) in a beaker and mixed for 1 minute. In a separate beaker, another sample of 210 ml of the resulting activated MFC solution is! also mixed with 15.5 grams of fine CaC03 and i was mixed for 1 minute. The contents of each beaker were then emptied into separate graduated cylinders of 100 ml and diluted to the 100 ml mark on each cylinder. In each case, the solutions exhibited excellent suspension properties and the solids (either sand or calcium carbonate) did not exhibit: precipitation from the target solution.

I Each of the graduated cylinders was then stored at room temperature (22-25 ° C) for 24 hours to determine if the precipitation occurred during that period of time. In each sample, after completing the 24 hours, the phase separations for the samples either from the top or bottom were less than 10% (by visual estimation), thus indicating excellent long-term suspension properties. Example 2 MFC was produced in a 1200 gal fermenter with a final yield of 1.49% weight. The broth was treated with 350 ppm of hypochlorite and subsequently treated with 70 ppm of lysozyme and 194 ppm of protease. A portion of the treated MFC broth was mixed with a given amount of xanthan gum broth (MFC / XG = 3/1, dry base) under high cut and the resulting mixture I was then precipitated with IPA (85%) to form a Pressed dough! The pressed mass was dried and ground as in Example 1. The powder formulation was then introduced into a STW sample in an amount of about 0.36% by weight thereof, with 20% by weight of CMC added simultaneously, and then the composition was mixed with Silverson nail at 8000 rpm for 10 minutes. The viscosity and yield stress of the product were 709 cP and 1.96 dynes / cm, respectively. Example 3 - - í MFC was produced in a 1200 gal fermenter with a final yield of 1.49% weight. The broth was treated with 350 f ppm of hypochlorite and subsequently treated with 70 ppm of I lysozyme and 194 ppm of protease. A portion of the treated MFC broth was mixed with a given amount of xanthan gum broth (MFC / XG = 4/1, dry base) under high cut and the resulting mixture was then precipitated with IPA (85%) to form a dough pressed. ' The pressed mass was dried and ground as in Example 1. The powder formulation was introduced into a STW sample in an amount of about 0.36% by weight thereof, with 20% by weight of CMC added simultaneously, and then the composition was mixed with a Silverson mixer at 8000 rpm for 10 minutes. The viscosity and yield stress of the product were 635 cP and J 1.54 dynes / cm, respectively. Example 4 'MFC was produced in a 1200 gal fermenter with a final yield of 1.49% weight. The broth was treated with 350 ppm of hypochlorite and subsequently treated with 70 ppm of lysozyme and 194 ppm of protease. A portion of the treated MFC broth was mixed with a given amount of xanthan gum broth (MFC /: XG = 3/1, dry base) and the resulting mixture was then precipitated with IPA (85%) to form a pressed mass. . The pressed mass was dried and ground as in Example 1. The powder formulation was introduced into ; - " a sample of STW in an amount of about 0.36% by weight of: 1a, with 10% by weight of CMC added simultaneously, and then the composition was mixed with a Silverson mixer at 8000 rpm for 10 minutes. The viscosity and flow stress of the product were 1242 cP and 4.5 dynes / cm2, respectively. Example 5, MFC was produced in a 1200 gal fermenter with a final yield of 1.49% weight. The broth was treated with 350 ppm of hypochlorite and subsequently treated with 70 ppm of lysozyme and 194 ppm of protease. A portion of the treated MFC broth was mixed with a given amount of xanthan gum broth (MFC / XG = 3/1, dry base) and the resulting mixture was then precipitated with IPA (85%) to form a pressed mass. The pressed mass was dried and ground as in Example 1. The powder formulation was introduced into a STW sample in an amount of about 0.36% by weight thereof, with 20% of CMC added simultaneously, and then the composition it was mixed with a Silverson mixer at 8000 rpm for 10 minutes. The viscosity and yield stress of the product were 1242 cP and 4.5 dynes / cm2, respectively. Example 6 j MFC was produced in a 1200 gal fermenter with a yield of 1.49 weight%. The broth was treated with 350 - - I ppm hypochlorite and subsequently treated with 70 ppm of lysozyme and 194 ppm of protease. A portion of the harvested MFC broth was mixed with a given amount of xanthan gum broth (MFC / ¡XG = 3/1, dry base) and the resulting mixture was then precipitated with IPA (85%) to form a pressed mass I . The pressed mass was dried and ground as in Example 1. The powder formulation was introduced into a STW sample in an amount of about 0.36% by weight of 1 thereof, with 20% by weight of CMC added simultaneously, and then the composition was activated with an I extensional homogenizer at 1500 psi during two passes. The measurements of viscosity and yield stress of the product were 1010 c-P and 1.76 dynes / cm2, respectively. Example 7! I MFC was produced in a 1200 gal fermenter with a final yield of 1.93% weight. The broth was treated with 350 ppm of hypochlorite and subsequently treated with 70 ppm of lysozyme and 1.94 ppm of protease. A portion of the treated MFC broth was mixed with a given amount of xanthan gum broth (MFC / XG = 3/1, dry base) and the resulting mixture was then precipitated with IPA (85%) to form a pressed mass. . The pressed mass was dried and ground as in Example 1. The powder formulation was introduced into a sample of STW in an amount of about 0.36% by weight thereof, with 20% by weight of added CMC. ! í í - - i I simultaneously, and then the composition was mixed with a Silverson mixer at 8000 rpm for 5 minutes. The viscosity and yield stress of the product were 690 cP and 2. 19 dynes / cm2 respectively. Example 8 MFC was produced in a 1200 gal fermenter with a final yield of 1.93% weight. The broth was treated with 350 ppm of hypochlorite and subsequently treated with 70 ppm of lysozyme and 19 ppm of protease. A portion of the treated MFC broth was mixed with a given amount of xanthan gum broth and CMC solution (MFC / XG / CMC = 3/1/1, dry base) and the resulting mixture was then precipitated with IPA (85%) to form a pressed sheet. The pressed mass was dried and ground as in Example 1. The powder formulation was introduced into a sample of STW in an amount of I about 0.36% by weight thereof, and then the composition was mixed with a Silverson mixer at 8000 rpm for 5 minutes. The viscosity and yield stress of the product were 1057 cP and 3.65 dynes / cm2, respectively. Example 9 MFC was produced in a 1200 gal fermenter with a final yield of 1.93% weight. The broth was treated with 350 i ppm hypochlorite and subsequently treated with 70 ppm lysozyme and 194 ppm protease. A portion of the treated MFC broth was mixed with a given amount of water solution.

I pectin (MFC / Bectin = 6/1, dry base) and the resulting mixture was then precipitated with IPA (85%) to form a pressed mass. The pressed dough was dried and ground as in Example 1. The powder formulation was introduced into a STW sample in an amount of about 0.36% by weight thereof, with 20% by weight of CMC added simultaneously, and then the composition was mixed with a Sil erson mixer at 8000 rpm for 5 minutes. The viscosity and yield stress of the product were 377 cP and 1.06 dynes / cm2, respectively. I Example 10 j MFC was produced in a 1200 gal. Therminator with a final yield of 1.93% weight. The broth was treated with 350 ppm of hypochlorite and subsequently treated with 70 ppm of lysozyme and 194 ppm of protease. A portion of the treated MFC broth was mixed with a given amount of CMC I solution (MFC / CMC = 3/1, dry base) and the resulting mixture was then precipitated with IPA (85%) to form a pressed mass. The pressed mass was dried and ground as in Example 1. The powder formulation was introduced into a sample of i STW in an amount of about 0.36% by weight thereof, and then the composition was mixed with a Silverson mixer. 8000 rpm for 5 minutes. The viscosity and yield stress of the product were 432 cP and 1.39 dynes / cm2, respectively.

, - - Example 11 MFC was produced in a 1200 gal fermenter with a final yield of 1.93% weight. The broth was treated with 350 was treated with 70 ppm of mixed a portion of the MFC broth treated with a given amount of pectin and CMC solutions (MFC / Pectin / CMC = 6 / l / 2, dry base) and the resulting mixture was then precipitated with IPA (85%) to form a pressed mass * The pressed mass was dried and crushed as in Example 1. The powder formulation was introduced into a STW sample in an amount of about 0.36% by weight thereof, and then the composition was mixed with a Silverson mixer at 8000 rpm for 5 minutes. The viscosity and yield stress of the product were 552 cP and I 1.74 dynes / cm ?, respectively. Example 12; MFC was produced in a 1200 gal fermenter with a final yield of 1.51% weight. The broth was treated with 350 ppm of hypochlorite and subsequently treated with 70 ppm of lysozyme and 350 ppm of protease followed by another 350 ppm of hypochlorite. : A portion of the treated MFC broth was mixed with a given quantity 1 of xanthan gum broth (MFC / XG = 2/1, dry base) then precipitated with IPA (85%), and then dried and ground as in Example 1. The powder formulation was introduced! then within a sample of STW in a - - amount of approximately 0.2% by weight thereof, with 10% of CMC added simultaneously, and then the composition was activated with an extensional homogenizer at 1500 psi for 2 passes. The viscosity of the product at 6 rpm was 377 cP. Example 13 j MFC was produced in a 1200 gal fermenter with a final yield of 1.6% weight. The broth was treated with 350 ppm of hypochlorite and subsequently treated with 70 ppm of lysozyme and 350 ppm of protease followed by another 350 ppm of hypochlorite. A portion of the MFC broth treated with j was mixed with a given amount of xanthan gum broth (MFC / XG = 2/1, dry base) then precipitated with IPA (85%), and then dried and triturated. as in Example 1. The powder formulation was introduced into a solution of deionized water, an STW solution and a 0.25% solution of CaCl2, respectively, in an amount of approximately 0.2% by weight; of the same, with 10% by weight of CMC added simultaneously, and then the composition was activated with an extensional homogenizer at 1500 psi for 2 passes. The product viscosities were 512 cP, 372 cP and 358 cP, in deionized water, STW and 0.25% CaCl2 solution, respectively. Analogous to the test carried out in Example 1, approximately 20 nylon beads of 3.2 mm in diameter were added by dripping with this wheel (each exhibiting - - i a density of approximately 1.14 g / ml) in each of the solutions (eri deionized water, STW or 0.25% solution of CaCl 2) and the 1 solutions were left at room temperature for 24 h. None of the beads settled on the bottom of the vessels after the expiration of the period of time, thus indicating excellent long-term suspension properties. EXAMPLE 14 MFC was produced in a 1200 gal. Thermenator with a final yield of 1.51% weight. The broth was treated with 350 ppm of hypochlorite and subsequently treated with 70 ppm of lysozyme and 35.0 ppm of protease followed by another 350 ppm of hypochlorite. j A portion of the treated MFC broth was mixed with a mixed amount of xanthan gum broth (MFC / XG = 2/1, dry base) then precipitated with IPA (85%), and then dried and crushed as in Example 1. The powder formulation was introduced into a sample of deionized water in an amount of about 0.2% by weight thereof, with 10% by weight of CMC added simultaneously, and then the composition was activated with a propeller mixer at 2500 rpm during ?? minutes The viscosity of the product was 185 i cP. , Example 15 j MFC was produced in a 1200 gal. Burner with a final yield of 1.4% weight. The broth was treated with 350 I í i i - - ppm of hypochlorite and subsequently treated with 70 ppm of lysozyme and 350 ppm of protease followed by another 350 ppm of hypochlorite. A portion of the treated MFC broth was mixed with a given amount of xanthan gum broth and pre-hydrated CMC solution! (MFC / XG / CMC = 6/3 / l, dry base) was then precipitated with IPA (85%), and then dried and triturated as in Example jl. The powder formulation was introduced into an STW solution and a 0.25% CaCl2 solution in an amount of about 0.2% by weight thereof, respectively, and then the composition was activated with a homogenizer; extensional to 1500 psi during 2 passes. The viscosities of the product at 6 rpm were 343 cP and 334 cP in STW solutions and 0.25% CaCl2, respectively. Approximately 20 nylon beads of 3.2 mm diameter (1.14 g / ml) were added dropwise in each of the solutions (in STW or 0.25% CaCl2 solution) and the solutions were left at room temperature for 24 hours. None of the beads settled in the bottom of the cups after the 24-hour time period. EXAMPLE 16 'MFC was produced in a 1200 gal. Thermenator with a final yield of 1.6% weight. The broth was treated with 350 ppm of hypochlorite and subsequently treated with 70 ppm of lysozyme and 350 ppm of protease followed by another 350 ppm of hypochlorite. j A portion of the treated MFC broth was mixed with i - - a given amount of pre-hydrated pectin and CMC solutions (MFC / Pectin / CMC = 6/3 / l, dry base) was then precipitated with IPA (85%), and then dried and triturated as in Example 1. The powder formulation was introduced into an STW solution and a 0.25% CaCl 2 solution in an amount of about 0.2% by weight thereof, i respectively, and then the composition was activated with a homogenizer < extensional to 1500 psi during 2 passes. The viscosities of the product at 6 rpm were 306 cP and 293 cP in STW solutions and 0.25% CaCl2, respectively. Approximately 20 nylon beads 3.2 mm in diameter (1.14 g / ml) in each of the solutions (in STW or 0.25% CaCl2 solution) were added dropwise and the solutions were left at room temperature during 24 hours. None of the beads settled on the bottom of the cups after the 24-hour time period. Example 17 (MFC was produced in a 1200 gal fermenter with a final yield of 1.6% weight.) The broth was treated with 350 ppm hypochlorite and subsequently treated with 70 ppm lysozyme and 350 ppm protease followed by another 350 ppm. hypochlorite: A portion of the treated MFC broth was mixed with a given amount of pre-hydrated CMC solution (MFC / CMC = 3/1, dry base) then precipitated with IPA (85%), and then dried and ground as in Example 1. The i j i - - The powder formulation was introduced into a STW solution i and a 0.25% solution of CaCl2 in an amount of about 0.2% by weight thereof, respectively, and then the composition was activated with an extensional homogenizer at 1500 psi for 2 hours. you pass The viscosities of the product at 6 rpm were 206 cP and 202 cP in STW solutions and 0.25% CaCl2, respectively. Approximately 20 nylon beads of 3.2 mm diameter (1.14 g / ml) were added dropwise in each of the solutions (in STW or 0.25% CaCl2 solution) and the solutions were left at room temperature for 24 hours. None of the beads settled on the bottom of the cups after the 24-hour time period. : Example 18 MFC was produced in a 1200 gal fermenter with a final yield of 1.54% weight. The broth was treated with 350 ppm of hypochlorite and subsequently treated with 70 ppm of lysozyme and 35 (0 ppm of protease followed by another 350 ppm of hypochlorite.) A portion of the treated MFC broth was mixed with a given amount of Diutan broth (MFC). / Diutan = 2/1, dry base) was then precipitated with IPA (85%), and then dried and triturated as in Example 1. The powder formulation was introduced into a solution of deionized water in a amount of approximately 0.2% by weight thereof, with 10% of CMC added simultaneously, and then the composition I I - - was activated with an extensional homogenizer at 1500 psi for 2 passes. The viscosity of the product at 6 rpm was 214 cP. Each! sample exhibited excellent and highly desirable results of viscosity modification and creep tension .. In terms of bacterial cellulose products, such results have hitherto been unattainable with bacterial cellulose materials alone and / or with the low complexity methods followed in the present invention. While the invention will be described and discussed in connection with certain preferred embodiments and practices, no attempt is made in any way to limit the invention to those specific embodiments, on the contrary, attempts are made to cover equivalent structures and all alternative modalities and modifications as it can be defined by the scope of the appended claims and equivalents thereof.

Claims (1)

1. CLAIMS A method for the production of a formulation containing bacterial cellulose comprising the steps of j a) providing a bacterial cellulose product; b) ppnally lysing the bacterial cells of the bacterial cellulose product; c) mixing said bacterial cellulose product either from step "a" or step "b" with a polymeric thickener selected from the group consisting of at least one charged cellulose ether, at least one precipitation agent, and any combination thereof; Y ? d) co-precipitating the mixture of step "c" with a non-water-miscible liquid in water. 2. The method of claim 1 wherein said polymeric thickener of step "c" is a charged cellulose ether. 3. The method of claim 2 wherein said charged cellulose ether is selected from the group consisting of sodium carboxymethyl cellulose, cationic hydroxyethyl cellulose, and any mixture thereof. 4. The method of claim 1 wherein said polymeric thickener of step "c" is a precipitating agent1. I 5. The method of claim 4 wherein said precipitating agent is selected from the group consisting of a xanthan product, pectin, alginates, gelatin gum, j welan gum, diutan gum, rhamsan gum, carrageenan, guar gum , agar, gum arabic, ghatti gum, karaya gum, tragacanth gum, tamarind gum, locust bean gum, and any mixture thereof. 6. The method of claim 1 wherein said bacterial cellulose product is a micro fibrillated cellulose. The method of claim 5 wherein said polymeric thickener of step "c" is a charged cellulose ether. The method of claim 7 wherein said charged cellulose ether is selected from the group consisting of sodium carboxymethylcellulose, cationic hydroxyethylceyulose, and any mixture thereof. 9. The method of claim 5 wherein said polymeric thickener of step "c" is a precipitating agent. 10. The method of claim 9 wherein said precipitating agent is selected from the group consisting of a product of xanthan, pectin, alginates, gelatin gum, diutan gum, welan gum, rhamsan gum, carrageenan, guar gum, agar, gum arabic, ghatti gum, karaya gum, tragacanth gum, tamarind gum, locust bean gum, and any mixture thereof. The method of claim 10 wherein said precipitating agent is selected from the group consisting of xanthan, pectin, diutan gum, and any mixture thereof; 12. A method for the production of a formulation containing bacterial cellulose comprising the steps of! a) provide a bacterial cellulose product; b) optionally lysing the bacterial cells of the bacterial cellulose product; c) mixing said resulting bacterial cellulose product from either step "a" or step "b" with at least one precipitation agent selected from the group consisting of a product of xanthan, pectin, alginates, gelatin gum, j welan gum, diutan gum, rhamsan gum, carrageenan, guar gum, agar, gum arabic, ghatti gum, karaya gum, tragacanth gum, tamarind gum, locust bean gum, and any mixture thereof; and d) co-precipitating the mixture of step "c" with a non-aqueous liquid miscible with water. 13. The method of claim 12 wherein said precipitation agent is selected from the group that consists of xanthene, pectin, diutan gum, and any mixture thereof! A method for the production of a formulation containing bacterial cellulose comprising the steps of a) providing a bacterial cellulose product; b) mixing said bacterial cellulose product with at least one precipitating agent selected from the group consisting of a product of xanthan, pectin, alginates, gelatin gum, welan gum, diutan gum, rhamsan gum, carrageenan, guar gum, agar, gum arabic, ghatti gum, karaya gum, tragacanth gum, tamarind gum, locust bean gum, and any mixture thereof; c) co-lysing the mixture of step "b" to remove bacterial cells therefrom; and d) co-precipitating the mixture of step "c" with a non-aqueous liquid miscible with water. 15. The method of claim 14 wherein said precipitating agent I is selected from the group consisting of xanthan, pectin, diutan gum, and any mixture thereof. A formulation containing bacterial cellulose which comprises at least one bacterial cellulose material and at least one polymeric thickener selected from the group consisting of at least one cellulose ether i charged, at least one precipitating agent, and any 1 mixture of them. same, wherein said formulation exhibits a viscosity capacity of at least 300 cps and a yield stress measurement of 1.0 dynes / cm2 when introduced in an amount of at most 0.36% by weight of a 500 ml sample of water and after the application of at most 2 passes at 1500 psi in urt extensional homogenizer. The formulation of claim 16 wherein said polymeric thickener is at least one charged cellulose ether. The formulation of claim 16 wherein said charged cellulose ether is selected from the group consisting of at least one sodium carboxymethyl cellulose, at least one cationic hydroxyethyl cellulose, and any mixture thereof. 19. The formulation of claim 16 wherein said polymeric thickener is a precipitating agent .; 20. The formulation of claim 19 wherein said precipitating agent is selected from the group consisting of a product of xanthan, pectin, alginates, gelatin gum, welan gum, rhamsan gum, carrageenan, gum and guar, agar, gum arabica, ghatti gum, karaya gum, tragacanth gum, tamarind gum, locust bean gum, and any mixture thereof. 21. The formulation of claim 16 wherein said bacterial cellulose product is micro fibrillated cellulose. 22. The formulation of claim 21 wherein both said charged cellulose ether and said precipitating agent are included. The formulation of claim 22 wherein said precipitating agent is selected from group i consisting of a product of xanthan, pectin, alginates, and gellan gum, welan gum, diutan gum, rhamsan gum, carrageenan, guar gum , agar, gum arabic, ghatti gum, karaya gum, gum tragacanth, tamarind gum, locust bean gum, and any mixture thereof. 24. The formulation of claim 23 wherein said charged cellulose ether is a sodium carboxymethyl Carbonate. The formulation of claim 24 wherein said precipitating agent is selected from the group consisting of xanthan, pectin, diutan gum, and any mixture thereof. 26.1 The formulation of claim 25 wherein said precipitating agent is xanthan. 27. The formulation of claim 25 wherein said precipitating agent is pectin. 28. The formulation of claim 25 in wherein said precipitating agent gum diutan. 29. The claim formulation wherein said xanthan precipitation agent. The formulation of claim 20 wherein said precipitating agent is pectin. 31. The formulation of claim 20 wherein said precipitating agent is diutan gum.